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US2666734A - Apparatus for conversion of residual oils - Google Patents

Apparatus for conversion of residual oils Download PDF

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US2666734A
US2666734A US167630A US16763050A US2666734A US 2666734 A US2666734 A US 2666734A US 167630 A US167630 A US 167630A US 16763050 A US16763050 A US 16763050A US 2666734 A US2666734 A US 2666734A
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chamber
pebble
conversion
conduit
oil
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US167630A
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Robert A Findlay
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Phillips Petroleum Co
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Phillips Petroleum Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/28Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
    • C10G9/30Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "moving bed" method
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/16Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "moving bed" method
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00Chemistry of hydrocarbon compounds
    • Y10S585/919Apparatus considerations
    • Y10S585/921Apparatus considerations using recited apparatus structure
    • Y10S585/922Reactor fluid manipulating device
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00Chemistry of hydrocarbon compounds
    • Y10S585/919Apparatus considerations
    • Y10S585/921Apparatus considerations using recited apparatus structure
    • Y10S585/924Reactor shape or disposition
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00Chemistry of hydrocarbon compounds
    • Y10S585/949Miscellaneous considerations
    • Y10S585/95Prevention or removal of corrosion or solid deposits

Definitions

  • V 1 This invention relates to the conversion of heavy residual oils. In one of its more specific aspects it relates to a method for cracking heavy residual oils at high temperatures; In another of its more specific aspects it relates to an improved system for cracking heavy residual oils at high temperatures. Heavy residual oils have long posed a considerable problem in the petroleum industry. Although the refining technique of the petroleum industry has improved j greatly during the past several years, heavy residual oils have been of little or no value because ofi'the very great tendency of such materials to form and deposit coke, tar, or other carbonaceous deposits in refining equipment. As the demand for petroleum products has increased, that demand has placed a greater burden upon thenatural resources of the world and has focused attention more directly uponfwhat heretofore has been deemed waste materials. Heavy residual oils are very closely akin to waste materials and v it is believed therefore that any process whichaids in the utilization of such materials is of very great importance. 7
  • this invention comprises heating a heavy residual hydrocarbon oil to a temperature above its initial boiling point, flashing the oil'so as to separate a vaporous phase and a liquid phase, passing the liquid. residual oil through an atomizing fog nozzle so asto .atomize the unvaporizable material into an exceedinglyfinely dispersed fog by the flow of the oil vapors.
  • the oilfog is then injected into the conversion chamber of pebble heater apparatus in which conversion chamber the pebbles are maintained at a temperature at least 'ashigh as the conversion temperature of the oil.
  • the oil ifog passes upwardly through the downfiowing I Zheated pebble mass and is converted to. form the idesired reaction products]
  • An object of this. invention is to provide an improved method for converting heavy residual gaseous material, such as ethylene.
  • Another object of the invention is to provide an improved system for cracking heavy residual oils. Another object of the invention is to provide a method for cracking heavy residual oil fog by heat treatment in pebble heater apparatus. Another object of the invention is to provide a method for producing substantially tarfree carbonblack from heavy residual oil fog. Another object of the invention is to provide a method for producing water gas from heavy residual oil fog. Another object of the invention is to overcomethe problem of coking in a process for converting heavy residual oils to carbon black and/orcoke, aromatic distillates,'and normally Other and further objects and advantages will be apparent to those skilled in the art upon study of the accompanying disclosure and the drawings.
  • pebbles Solid heat exchange material which may be utilized in the pebble heater system of this invention is generaly termed pebbles.
  • pebbles as used herein denotes any substantially solid material of flowable size and formv which has sufiicient strength 'to withstand mechanical pressures and the temperatures encountered within the pebble heater system. These pebbles must be of such structure that they can carry large amounts of heat from one chamber to another without rapid deterioration of substantial breakage.
  • Pebbles which may be satisfactorily used in this gasification system may be substantially spherical in shape and range from about one-eighth inch to about one inch in diameter. The pebbles are preferably of a size within the range of from one-eighth inch to five-eighths inch in diameter.
  • Materials which maybe used singly orin combination in the formation of such pebbles include among others alumina, silicon carbide, periclase, beryllia, mullite, nickel, cobalt, copper, 'iron, magnesia, and silica. v
  • Figure 1 is a diagrammatic elevation, partly in section, of the conversion sys-: tem of this invention.
  • Figure 2 is a flow diagram showing the flow of materials in the conversion of heavy residual oils to carbon black and/or coke, aromatic distillates, and normally gaseous products.
  • Figure 3 is a schematic elevation'of a preferred modification of the conversion chamber of this invention.
  • Figure 4 is affiow diagram showing a modification of thisinvention; I
  • 'furnace t I is provided with an oil inlet conduit l2 having a flow control valve l3 provided therein.
  • Steam inlet conduit l4, having a flow control valve I5 provided therein, extends into furnace H and is connected to heating coils it within the furnace.
  • Heated 5 oil conduit l'l extends between coil l5 and flash chamber 18.
  • Flow control valve is is provided in conduit i! to regulate the fiowof fluid therethrough.
  • Flash chamber I8 is provided in its upper end portion with vapor outlet conduit 2t :10 which has flow control valve 22 provided therein, Residual oil outlet conduit 23 extends-from.;the; lower end portion of flash chamber i8 and is divided into a plurality of-residual oil.
  • conduits schematically shown as conduits 24: and 25;wh-ich':1 conduits have positioned therein flow control valves 2'6 and 21, respectively.
  • is connected to vapor conduit 28 which has positioned in its outlet end portions atomiziing fog nozzles 29.
  • is connected to vapor conduit 28 and has .fiow control valve 32 positioned therein.
  • Fog nozzles 29 have their outlet ends extending into conversion chamber 25 33 of pebble heater apparatus.
  • a pebble support member 34 extends inwardly from the wall of conversion chamber 33 to a point spaced a substantial distance from the wall of that chamber.
  • Pebble support 34 may be a frusto conical member or a memberof any other shape which will provide a sufiicient amount of void space around a portion of the pebbles to allow the oil fog to be properly distributed.
  • the support member is provided with a large num- 35 ber of perforations 35 which are of such size .as" to allow the passage of oil fog and any diluent vapors therethrough but which will prevent the passage of pebbles therethrough.
  • a relatively large pebble throat is formed in the'central part 40 ofpebble support member 34 'andpermits the passage of pebbles therethrough. Flushing .gas
  • inlet conduits 36 which have flow control valves 3? provided therein, extend intoconversion chamber 33 at pointsadjacent the lowerside of 5 pebble support member 34.
  • positioned above conversion chamber.-33, is connected to chamber 33 by a throat member 42, which throat member is adapted to allow pebbles to pass therethrough bygravitation.
  • Sealing gas inlet'conduit 43 is connected to throat 42 intermediate itsends.
  • Heating material-inlet conduit 44 is connected to the lower end portion of pebble heater chamber 4
  • is provided with an eiiluent outlet conduit 45 and pebble inlet conduit 46 in its upper endv portion.
  • Diluent inlet conduit 41 is provided in thelower-portion of conversion 90 chamber 33 and pebble outlet: conduit- 48 ex-.
  • Effluent outlet conduit 54 is connected at its outlet end-;..to.-;a centrifugal-type separator 55 and is connected; intermediate its ends, with a quench material inlet conduit 56 provided with :jlfiyfi-OW control valve 51 therein.
  • Outlet conduit 53 is provided in the lower portion of separator 55.:t :allowthe removal of heavy materials therefrom;
  • Gaseous material outlet conduit 59 extendsefrom'apomtintermediate the ends of separator- -55;;thr ough the upper portion of separator 55 and is-connected-at its outlet end to scrubber 5i. Conduit, 59 is.
  • a by-pass conduit"63 which is. preferably an, electrostatic separator.
  • Separatorv 65 is provided with an outlet conduit 66 in. its lower. end portion, which outlet conduit allows vthe removal. of .heavy material, such as carbon black, from separator 65.
  • Gaseous material outlet conduit 61 having new control valve 68 provided .therein, extends..from separator 65 at a point intermediate its..ends.
  • Conduit 15' extends between the up er portion of settler. chamber 13, and cooler 16.
  • Conduit ll-"extendsfrom. cooler. 161to convey the cooled products therefrom, andis... provided with flow control. valve '18 therein.
  • Operation by meansof the preferred process or.v method of this. invention permits the economicalconversion of heavy residual oil to normally lighter materials which include highly aromaticgasolines,
  • A. readilyv combustible fuel,. together with air or a hot'heat exchange gas is introduced into the lower portionof pebble heater chamber. 4
  • Ha fuel'and air are introduced into the lower portion. ofchamber 4
  • a hot heat exchange gas is utilized, it is introduced into pebble. heater chamber 4
  • When heavy residual oils are convertedfto normally gaseous materials. or highly aromatic; gasoline constitients, reaction..-temperatures; between 1000 F.
  • pebble heater chamber H to a temperaturebetween.about..120(l. E. andv 1700 F.
  • Heavy residual oil is introduced by means of conduit l2 into furnace H and is heated'th'erein to a temperature above its initial boiling point.
  • the heated oil is passed to flash chamber I8 in which the vaporous materials are flashed from the unvaporized materials and are removed from the upper portion of flash chamber I8 through outlet conduit 2
  • the heated oil is' flashed in chamber l 8 at such a pressure that the vaporized portion is passed to nozzles 29 under suflicient pressure to atomize the unvaporized material.
  • the unvaporized' oil is removed from'the lower portion of flash chamber is through conduit 23 and is passed to fog atomizing nozzles 29 by. means of conduits 24 and 25.
  • the vaporous oil materials are passed to the fog nozzles 29 through conduits 2! and 28 and atomize the un-' vaporized oil so as to form a finely dispersed oil fog which is immediately introduced into the void space in conversion chamber 33 immediately below pebble support member 34.
  • pebble support member 34 prevents the pebbles from fillin'g conversion chamber 33 to the outlet end of fog nozzles 29, thus providing the void space into which the oil fog is introduced.
  • the oil fog is evenly distributed throughout the void space and passes upwardly through the perforations 35 -and through the pebble opening in the central portion of support member 34 into the upper portion of conversion chamber 33 countercurrent to the flow of pebbles therethrough. Since the descending pebbles are hotter than the oil fog, the pebbles tend to repel the tiny fog particles because of normal expansion of gas away from the pebbles.
  • the fog particles and gaseous reactants pass upwardly through the pervious pebble mass, being heated to the cracking temperature with concomitant conversion thereof.
  • Pebbles which have been cooled in the heat exchange within chamber 33 are positively fed from the lower portion of conversion chamber 33 to elevator 5
  • steam has been specifically described as being the diluent material utilized in the oil fog conversion process of this invention
  • gaseous diluent materials such as methane, hydrogen, and the like, which are inert to the conversion process may also be utilized with excellent results.
  • the conversion of heavy residual oil in the manner above described results in the production of between about 25 and 50 per cent by weight of normally gaseous materials in relation to the feed.
  • the resulting product gas stream from the conversion is very rich in olefinic and aromatic materials, such as ethylene, propylene, and highly aromatic gasoline constituents
  • a quench material such as a gas oil or the like is introduced into conduit 54 through conduit 56 and the temperature of the reaction products is lowered to a temperature 7 within the range of about 300 F. to 800 F., preferably 400 F. to 500 F.
  • the quenched products, together with the quench liquid, are introduced tangentially into separator 55 and the gaseous materials are separated from tarry and carbonaceous materials which are condensed as a result of the quench step.
  • the heavier materials are removed from separator 55 through outlet conduit 58 and the gaseous materials are passed by means of conduit 59 into the lower portion of scrubber 0
  • the gaseous materials flow upwardly through the scrubber and any further tarry materials, carbonaceous materials, or liquid hydrocarbons which are condensed therein are washed from the gaseous products.
  • the gaseous materials are removed from the upper portion of the scrubber and are passed to product separa tion means, not shown.
  • the wash liquid, together with condensed liquid and solids, are passed to a settler from which solid materials, such as coke and tar, and water are settled out and are removed through conduit 14.
  • the wash liquid containing condensed hydrocarbons is purified thereby and is then passed to a cooler so as to lower its temperature. A portion of the cooled wash liquid is then returned to the upper portion of the wash chamber and a portion of the liquid is removed as additional liquid prodduct of the reaction.
  • Conversion chamber is'formed with lower portion 86 which is expanded or of greater diameter than'the upper chamber portion.
  • Fog nozzles 29 extend into the upper end'of conversion chamber portion 86.
  • the expanded chamber portion provides a space in its upper end which is void ofpebbles. during pebble-now through the chamber.
  • the method of operating chamber 85' is the sameas-that-utilized incomiection with chamber-'33-except that-the oil fog isintroduced into the lower-conversion chamber portion at a point adjacent therlower end of the upper conversion chamber portion. Further description of the method of operation istherefore deemed to be unnecessary.
  • Pebbles are heated t-l300" F. in a pebble heating zone and are gravitated into the upper portion of a conversion zone at a rate of '70 pounds per pound of oil feed and the pebbles form a fluent contiguous mass within the conver sion zone.
  • a 14 APIresiduum having a Saybolt Furol viscosity at 122 F. of 820; having an initial boilingpoint of 82Q F., and a per cent distillation point at 912 R, is heated and flashed at a. temperature between 850 F. and 950 F.
  • cent of normally gaseous material based upon the feed, is obtained with a coke .deposition on the pebbles of between 5 and weight per cent.
  • Steam is introduced into the lower portion of the conversion zone at a rate of between 2 and 5 pounds of steam per pound of oil.
  • Gaseous effiuent is removed from the conversion chamber at about 1160 F. and pebbles are removed from the conversion chamber at about 735 F.
  • the product gas has a composition in moi per cent as set forth-in the table.
  • the resultin gasoline. product has an API gravity of 49.2 and an aniline point of 3l.2"- F.
  • the process of this invention is particularly adapted to the production of olefins; This is especially carbon and light gaseous hydrocarbons.
  • the process which has-been described above is modified by'raising'the temperature within the conversion chamber to between 2000 F. and 2400 F. At a, temperature within thisrange the oil fog is uniformly spread over the area of the conversion chamber but the temperature is so high that: the hydrocarbon oil is cracked to form Steam which is injected into the conversion chamber 33 through inlet, conduits 47', 36, 28,-and 52 reacts with the carbonaceous material to form CO, H2, and CO2 by the well known water gas reaction. The following reactions take place upon passing steam over carbon at. a temperature within the above specified temperature range.
  • a still further modification of thisinvention is made when it is desired to convert the heavy residual oils to form carbon black.
  • a diluent materiaL such as hydrogen or methane, isintroduced into conversion chamber 33 throughinlet conduit 41.
  • the product efiiuent is removed fromthe upper portion of conversion chamber 33 through 'efiluent conduit 54 and a quench material, such as water or methane, is utilized to lower the temperature of the efiiuent stream to a temperature between about 900 F. and 1100 F.
  • a quench material such as water or methane
  • the reaction product stream, together with the quench material, ' is introduced tangentially into separator 55 and heavy materials which are separated from the gas stream are removed therefrom through outlet conduit 58.
  • Flow control valve 62 is closed and flow control valve 64 is opened so that the gaseous material which is removed from separator 55 through conduit 59. passes by way of' conduit '63 to electrostatic separator 65.
  • The'carbon black is electrostatically precipitated from the gas stream within separator 65 and.
  • conduit 66 is removed therefrom by means of conduit 66.
  • the remaining gaseous products and, quench material are removed from separator 65 through conduit 61 and are passed to manufacture of water gas as well as others heretofore set-forth.
  • Pebbles which are at such a high temperature are verydiflicult to recycle from a conversion chamber to a pebble heatingchamber.
  • the amount of fluid material which is introduced .into thelower portion of the conversion chamber as a diluent can be varied so as to control the temperature of the recycled pebbles.
  • the process of this invention may be varied advantageously by utilizing only the flashed vapors as reactant materials and using those vapors to atomize a water stream so as to distribute the water particles through the lower portion of the conversion chamber.
  • pebbles are heated in chamber 4
  • the pebbles are separated from the walls of a lower portion of the conversion chamber so as to form a void space therein.
  • Hydrocarbon vapors are introduced into fog nozzles 29 as described above. Water is introduced into fog nozzles 29 through conduit 9
  • the water is atomized by the vapor stream and the water particles, together with the hydrocarbon vapors, are introduced intothe void space formed in the lower portion of conversion chamber 33.
  • the water particles are converted to steam within the lower portion of conversion chamber 33 and the steam, together with the hydrocarbon vapors,
  • a quench material such as water, is introduced into gaseous eflluent outlet conduit 54 through conduit 92 and the resulting mixture of fluids is introduced into separation chamber 93 where coke and tar are removed from the stream, The coke and tar are removed through v outlet conduit 94 in the lower portion thereof.
  • the fluid stream is removed from chamber 93 and passed by a continuation of conduit 54 into cooler chamber 95 in which the stream is passed in heat exchange relation with a coolant fluid.
  • the cooled stream is passed by further continuation of conduit 54 through condenser chamber 96 in which the eflluent stream is further cooled so as to condense the gaseous materials.
  • the necessity for this condenser chamber will depend upon the amount of cooling obtained in cooler chamber 95.
  • the eifluent fluid stream is introduced into sepacon d uit 4ii.
  • This type of operation has many advantages turned to the uppefportion of pebble heater chamber 4
  • a considerably greater amount of heat is removed from the-pebbles by the conversion of water to steam "within the conversion chamber than wouldfbe obtained by the introduction of a similar amount of steam into that chamber. It is thus possible “to utilize very high temperatures within the conversionchamber and yet lower the temperature of those pebbles before it is necessary to handle them in the recycle system to the pebble heater chamber. Very high thermal efliciency of the pebble heater system is therefore obtained by conversion chamber is condensed and circulated,
  • An improved residuum conversion system comprising an upright pebble heater chamber having pebble inlet means and efliuent outlet means in its upper end portion; heating material inlet means in the lower portion of said pebble heater chamber; an upright conversion chamber disposed below said pebble heater chamber; a pebble conduit extending between the lower end portion of said pebble heater chamber and the upper end portion of said conversion chamber; a perforate pebble support member extending inwardly from the wall of said conversion chamber at a level intermediate its ends, said pebble support member providing a pebble passage centrally therethrough; pebble outlet means in the lower portion of said conversion chamber; an elevator extending from said pebble outlet means in said conversion chamber to said pebble inlet means in said pebble heater chamber; at least one fog nozzle extending through the wall of said conversion chamber and adjacent the lower side of said pebble support member; an oil residuum heating chamber having residuum conduit means extending therethrough; a flash chamber; a conduit extending from said residuum conduit means

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

2 Sheets-Sheet 1 R. A. FINDLAY APPARATUS FOR CONVERSION OF RESIDUAL OILS Jan. 19, 1954 Flled June 12, 1950 FIG. 3.-
PRODUCT STEAM STEAM r r ll v l4 STEAM HEAVY OIL INVENTOR.
R.A\ FINDLAY WM/w 2| OIL VAPOR FIG.
- ATTORNEYS Patented Jan. 19, 1954 APPARATUSFOR. CONVERSION OF I RESIDUAL on.s
Robert A. Findlay, Bartlesville, kla., asslgnor toPhillips Petroleum Company, a. corporation of Delaware Application June 12, 1950, Serial No. 167,630
V 1 This invention relates to the conversion of heavy residual oils. In one of its more specific aspects it relates to a method for cracking heavy residual oils at high temperatures; In another of its more specific aspects it relates to an improved system for cracking heavy residual oils at high temperatures. Heavy residual oils have long posed a considerable problem in the petroleum industry. Although the refining technique of the petroleum industry has improved j greatly during the past several years, heavy residual oils have been of little or no value because ofi'the very great tendency of such materials to form and deposit coke, tar, or other carbonaceous deposits in refining equipment. As the demand for petroleum products has increased, that demand has placed a greater burden upon thenatural resources of the world and has focused attention more directly uponfwhat heretofore has been deemed waste materials. Heavy residual oils are very closely akin to waste materials and v it is believed therefore that any process whichaids in the utilization of such materials is of very great importance. 7
Many processes have been set forth in the petroleum art by which it has beenrproposed to crack heavy residual oils to provide normally lighter materials, such as hydrogen and hydro- I ampons and gasoline stocks; As pointed out above, however, the tendency for such materials to form carbonaceous deposits has made such processes relatively uneconomical. I have devised a process and a system whereby the tendency of such heavy, residual' oils .toyformtarry and carbonaceous materials maybe considerably overlooked becausesuchmaterials are handled in this process with minimum detrimental efiects.
Broadly V speaking, this invention comprises heating a heavy residual hydrocarbon oil to a temperature above its initial boiling point, flashing the oil'so as to separate a vaporous phase and a liquid phase, passing the liquid. residual oil through an atomizing fog nozzle so asto .atomize the unvaporizable material into an exceedinglyfinely dispersed fog by the flow of the oil vapors. The oilfog is then injected into the conversion chamber of pebble heater apparatus in which conversion chamber the pebbles are maintained at a temperature at least 'ashigh as the conversion temperature of the oil. The oil ifog passes upwardly through the downfiowing I Zheated pebble mass and is converted to. form the idesired reaction products] An object of this. inventionis to provide an improved method for converting heavy residual gaseous material, such as ethylene.
5 Claims; (Cl. 196-120) oils. Another object of the invention is to provide an improved system for cracking heavy residual oils. Another object of the invention is to provide a method for cracking heavy residual oil fog by heat treatment in pebble heater apparatus. Another object of the invention is to provide a method for producing substantially tarfree carbonblack from heavy residual oil fog. Another object of the invention is to provide a method for producing water gas from heavy residual oil fog. Another object of the invention is to overcomethe problem of coking in a process for converting heavy residual oils to carbon black and/orcoke, aromatic distillates,'and normally Other and further objects and advantages will be apparent to those skilled in the art upon study of the accompanying disclosure and the drawings.
Solid heat exchange material which may be utilized in the pebble heater system of this invention is generaly termed pebbles." The term pebbles as used herein denotes any substantially solid material of flowable size and formv which has sufiicient strength 'to withstand mechanical pressures and the temperatures encountered within the pebble heater system. These pebbles must be of such structure that they can carry large amounts of heat from one chamber to another without rapid deterioration of substantial breakage. Pebbles which may be satisfactorily used in this gasification system may be substantially spherical in shape and range from about one-eighth inch to about one inch in diameter. The pebbles are preferably of a size within the range of from one-eighth inch to five-eighths inch in diameter. Materials which maybe used singly orin combination in the formation of such pebbles include among others alumina, silicon carbide, periclase, beryllia, mullite, nickel, cobalt, copper, 'iron, magnesia, and silica. v
More complete understanding of the invention will be obtained upon reference to the schematic drawings in which Figure 1 is a diagrammatic elevation, partly in section, of the conversion sys-: tem of this invention. Figure 2 is a flow diagram showing the flow of materials in the conversion of heavy residual oils to carbon black and/or coke, aromatic distillates, and normally gaseous products. Figure 3 is a schematic elevation'of a preferred modification of the conversion chamber of this invention. Figure 4 is affiow diagram showing a modification of thisinvention; I
Referring particularly to'the device shown as Figure 1 of the drawings, 'furnace t I is provided with an oil inlet conduit l2 having a flow control valve l3 provided therein. Steam inlet conduit l4, having a flow control valve I5 provided therein, extends into furnace H and is connected to heating coils it within the furnace. Heated 5 oil conduit l'l extends between coil l5 and flash chamber 18. Flow control valve is is provided in conduit i! to regulate the fiowof fluid therethrough. Flash chamber I8 is provided in its upper end portion with vapor outlet conduit 2t :10 which has flow control valve 22 provided therein, Residual oil outlet conduit 23 extends-from.;the; lower end portion of flash chamber i8 and is divided into a plurality of-residual oil. conduits schematically shown as conduits 24: and 25;wh-ich':1 conduits have positioned therein flow control valves 2'6 and 21, respectively. Vapor outlet conduit 2| is connected to vapor conduit 28 which has positioned in its outlet end portions atomiziing fog nozzles 29. Diluent fluid conduit 3| is connected to vapor conduit 28 and has .fiow control valve 32 positioned therein. Residual oil conduits 24 and are connected at their outlet ends to fog nozzles 29. Fog nozzles 29 have their outlet ends extending into conversion chamber 25 33 of pebble heater apparatus.
. A pebble support member 34 extends inwardly from the wall of conversion chamber 33 to a point spaced a substantial distance from the wall of that chamber. Pebble support 34-may be a frusto conical member or a memberof any other shape which will provide a sufiicient amount of void space around a portion of the pebbles to allow the oil fog to be properly distributed. The support member is provided with a large num- 35 ber of perforations 35 which are of such size .as" to allow the passage of oil fog and any diluent vapors therethrough but which will prevent the passage of pebbles therethrough. A relatively large pebble throat is formed in the'central part 40 ofpebble support member 34 'andpermits the passage of pebbles therethrough. Flushing .gas
inlet conduits 36, which have flow control valves 3? provided therein, extend intoconversion chamber 33 at pointsadjacent the lowerside of 5 pebble support member 34. I
Pebble heating chamber 4|, positioned above conversion chamber.-33, is connected to chamber 33 by a throat member 42, which throat member is adapted to allow pebbles to pass therethrough bygravitation. Sealing gas inlet'conduit 43 is connected to throat 42 intermediate itsends. Heating material-inlet conduit 44 is connected to the lower end portion of pebble heater chamber 4| and provides means .for introducing fuel or 'hot gaseous heat exchange material into'chamber 4|. Chamber 4| is provided with an eiiluent outlet conduit 45 and pebble inlet conduit 46 in its upper endv portion. Diluent inlet conduit 41 is provided in thelower-portion of conversion 90 chamber 33 and pebble outlet: conduit- 48 ex-. tends downwardly from the'lower' end of conversion'chamber 33. A- nositive-pe ble flow control means, such as pebble=feeder49.- is provided intermediate the ends ofpebble outlet conduit 55 48. Elevator 5| extends between the outlet end of; pebble conduit 4*; and the inlet end of ebble conduit 46. A flush ng gas-in et con uit 52 having a flow"-'control valve 53-nrovided there n ex-, tendsinto the up er end of'conversion chamber 7 33.:and' is preferably in the form ofa perforate header disposed adjacent the upper end of chainber 33 and about the eflluent outlet: Gaseous efiiuent outletconduit 54 extends fromthe-upp end. of. conversion. chamber:- 3.3. and pro des-I 4 1 means of escape for reaction products from reaction chamber 33.
Referring particularly to Figure 2 of the drawings, like numerals are utilized to designate like parts which are shown in Figure 1 of the drawings. Effluent outlet conduit 54 is connected at its outlet end-;..to.-;a centrifugal-type separator 55 and is connected; intermediate its ends, with a quench material inlet conduit 56 provided with :jlfiyfi-OW control valve 51 therein. Outlet conduit 53 .is provided in the lower portion of separator 55.:t :allowthe removal of heavy materials therefrom; Gaseous material outlet conduit 59 extendsefrom'apomtintermediate the ends of separator- -55;;thr ough the upper portion of separator 55 and is-connected-at its outlet end to scrubber 5i. Conduit, 59 is. provided with a flow control valve 62intermediate its ends. A by-pass conduit"63,'.. having flow control valve 64 provided therein, extends from conduit 59 at a point upstreamof flow control valve 62to separator 55 whichv is. preferably an, electrostatic separator. Separatorv 65 .is provided with an outlet conduit 66 in. its lower. end portion, which outlet conduit allows vthe removal. of .heavy material, such as carbon black, from separator 65. Gaseous material outlet conduit 61, having new control valve 68 provided .therein, extends..from separator 65 at a point intermediate its..ends. Gaseous material outlet conduit .69, having flow control valve ii provided. therein; extends .fromthe upper end of'scrubberti. andisconnected to conduit 61 at. a. point downstream of. flow control valve ll. Liquid 'outlet'conduit 12. extendsfrom the lower portion vof; scrubber 61. to. a. settler chamber 13. Outlet conduit" is provided inthe lower end portion of jsettlerchamber. 13 to allow the removal of heavy materialsfrom that chamber. Conduit 15' extends between the up er portion of settler. chamber 13, and cooler 16. Conduit ll-"extendsfrom. cooler. 161to convey the cooled products therefrom, andis... provided with flow control. valve '18 therein. Conduit i9, having flow control'valve. 8| provided therein, extends from conduit 11' upstream offlow control valve 'ld'tothe, upper portion of scrubber 6|. Conduit 82,- for makeeup washingjliquid" and having flow control valve 83 provided" therein, is connected to conduit 19. downstream ofifiow control valve 8]..
Operation by meansof the preferred process or.v method of this. invention, permits the economicalconversion of heavy residual oil to normally lighter materials which include highly aromaticgasolines, A. readilyv combustible fuel,. together with air or a hot'heat exchange gas is introduced into the lower portionof pebble heater chamber. 4| through inlet conduit 44. Ha fuel'and air are introduced into the lower portion. ofchamber 4|, that fuel'is burned in the presenceofa contiguous mass of pebbles which are gravitated downwardly therethrough, thus raising the temperature of the pebbles to the desiredreaction temperature. If a hot heat exchange gas is utilized, it is introduced into pebble. heater chamber 4| through conduit id andjthe hot heat, exchange gas is passed upwardly" through that chamber countercurrent to the. flow. Qt pebbles therein. When heavy residual oils are convertedfto normally gaseous materials. or highly aromatic; gasoline constitients, reaction..-temperatures; between 1000 F.
and 1500 F. are ordinarily utilized. The pebbles are thus heated in pebble heater chamber H to a temperaturebetween.about..120(l. E. andv 1700 F.,
depending upon the amount of'diluent' utilized in the conversion chamber, and are gravitated into the upper portion of conversion chamber 33 in which they form a hot fluent contiguous mass.
Heavy residual oil is introduced by means of conduit l2 into furnace H and is heated'th'erein to a temperature above its initial boiling point.
' The heated oil is passed to flash chamber I8 in which the vaporous materials are flashed from the unvaporized materials and are removed from the upper portion of flash chamber I8 through outlet conduit 2|. The heated oil is' flashed in chamber l 8 at such a pressure that the vaporized portion is passed to nozzles 29 under suflicient pressure to atomize the unvaporized material. The unvaporized' oil is removed from'the lower portion of flash chamber is through conduit 23 and is passed to fog atomizing nozzles 29 by. means of conduits 24 and 25. The vaporous oil materials are passed to the fog nozzles 29 through conduits 2! and 28 and atomize the un-' vaporized oil so as to form a finely dispersed oil fog which is immediately introduced into the void space in conversion chamber 33 immediately below pebble support member 34.
As stated above, pebble support member 34 prevents the pebbles from fillin'g conversion chamber 33 to the outlet end of fog nozzles 29, thus providing the void space into which the oil fog is introduced. ,The oil fog is evenly distributed throughout the void space and passes upwardly through the perforations 35 -and through the pebble opening in the central portion of support member 34 into the upper portion of conversion chamber 33 countercurrent to the flow of pebbles therethrough. Since the descending pebbles are hotter than the oil fog, the pebbles tend to repel the tiny fog particles because of normal expansion of gas away from the pebbles. The fog particles and gaseous reactants pass upwardly through the pervious pebble mass, being heated to the cracking temperature with concomitant conversion thereof. Such fog particles as strike the pebbles simply form coke thereon, which'coke is thereafter removed from the pebbles in the pebble heating chamber byoxidation with an excess of oxygen in that chamber. Reaction products are removed. from conversion chamber 33 through eiliuent outlet conduit 54. I 4
I have found that it is quite advantageous in this process to utilize a diluent material which aids in maintaining a high dispersion of the oil fog. The steps which have been described above are usually modified by the introduction of a diluent such as steam, through conduit l4 into heating coils IS in furnace II. The steam is flashed in flash chamber l8, together with vaporized oil material, and is passed through conduits 2| and 28 into fog nozzles 29. Additional steam is added throughf conduit'3l 'to aid in atomizing and dispersingv the unvaporized oil material removed from the lower portion of flash chamber [8. Deposit of carbon .upon pebble support member 34 is greatly reduced byintroducing streams of steam along the lower surface of support member 34 through steam conduits 35. Deposit of carbonaceous materials in the upper end of conversion chamber 33 about. the effluent outlet conduit is also substantially reduced by maintaining a blanket of steam thereupon, which steam is introduced through conduit 52. Additional diluent material is normally added at the lower portion of conversion chamber 33', which diluent material passes upwardly through the pebble mass and through pebble support member 34. Diluent is advantageously introduced into the conversion chamber in a ratio of between 0.5:1 to 4:1 in relation to the oil.
Pebbles which have been cooled in the heat exchange within chamber 33 are positively fed from the lower portion of conversion chamber 33 to elevator 5| by which means the pebbles are elevated to the upper portion of pebble heater chamber 4|. 7
Although steam has been specifically described as being the diluent material utilized in the oil fog conversion process of this invention, other gaseous diluent materials such as methane, hydrogen, and the like, which are inert to the conversion process may also be utilized with excellent results.
The conversion of heavy residual oil in the manner above described results in the production of between about 25 and 50 per cent by weight of normally gaseous materials in relation to the feed. The resulting product gas stream from the conversion is very rich in olefinic and aromatic materials, such as ethylene, propylene, and highly aromatic gasoline constituents Referring again particularly to the flow diagram shown as Figure 2 of the drawings, the conversion products are passed by means of conduit 54 to separator 55. A quench material such as a gas oil or the like is introduced into conduit 54 through conduit 56 and the temperature of the reaction products is lowered to a temperature 7 within the range of about 300 F. to 800 F., preferably 400 F. to 500 F. The quenched products, together with the quench liquid, are introduced tangentially into separator 55 and the gaseous materials are separated from tarry and carbonaceous materials which are condensed as a result of the quench step. The heavier materials are removed from separator 55 through outlet conduit 58 and the gaseous materials are passed by means of conduit 59 into the lower portion of scrubber 0| through which a circulating oil wash is gravitated. The gaseous materials flow upwardly through the scrubber and any further tarry materials, carbonaceous materials, or liquid hydrocarbons which are condensed therein are washed from the gaseous products. The gaseous materials are removed from the upper portion of the scrubber and are passed to product separa tion means, not shown. The wash liquid, together with condensed liquid and solids, are passed to a settler from which solid materials, such as coke and tar, and water are settled out and are removed through conduit 14. The wash liquid containing condensed hydrocarbons is purified thereby and is then passed to a cooler so as to lower its temperature. A portion of the cooled wash liquid is then returned to the upper portion of the wash chamber and a portion of the liquid is removed as additional liquid prodduct of the reaction.
Referring particularly to Figure 3 of the drawings, like numerals are utilizedto designate parts similar to those described" in connection with Figure 1 of the drawings. Conversion chamber is'formed with lower portion 86 which is expanded or of greater diameter than'the upper chamber portion. Fog nozzles 29 extend into the upper end'of conversion chamber portion 86. The expanded chamber portion-provides a space in its upper end which is void ofpebbles. during pebble-now through the chamber. In. his type of chambeutherefore;it-is not necessary to utis lize a pebblesuppqrt member such as is disclosed inv the d v ce. ifu es-lan -zl u h n as inlet conduits 36. extend; into chamber portion 5% above the level of nozzles 29.
The method of operating chamber 85' is the sameas-that-utilized incomiection with chamber-'33-except that-the oil fog isintroduced into the lower-conversion chamber portion at a point adjacent therlower end of the upper conversion chamber portion. Further description of the method of operation istherefore deemed to be unnecessary.
Aspecificembodiment of this invention is set forth inthe example below but it is not intended to -limit the scopeof this invention thereby.
EXAMPLE Pebbles are heated t-l300" F. in a pebble heating zone and are gravitated into the upper portion of a conversion zone at a rate of '70 pounds per pound of oil feed and the pebbles form a fluent contiguous mass within the conver sion zone. A 14 APIresiduum having a Saybolt Furol viscosity at 122 F. of 820; having an initial boilingpoint of 82Q F., and a per cent distillation point at 912 R, is heated and flashed at a. temperature between 850 F. and 950 F. The
cent of normally gaseous material, based upon the feed, is obtained with a coke .deposition on the pebbles of between 5 and weight per cent. Steam is introduced into the lower portion of the conversion zone at a rate of between 2 and 5 pounds of steam per pound of oil. Gaseous effiuent is removed from the conversion chamber at about 1160 F. and pebbles are removed from the conversion chamber at about 735 F. The product gas has a composition in moi per cent as set forth-in the table.
Table Gas composition: Mol per cent Hydrogen Y 14 C1 22 Ethylene 38 Ethane 3 Propylene 14 Propane 0.7 Buteries. 8 Butane l- 0.3
lowing composition:
Liquid product composition; Volume per cent Gasoline p 22.5
ight gasoil, 750 it. PM 1 2.9 Heavy gas il. 00.. E..- 1 -7 Residuum (tars, etc.) 46.9
The resultin gasoline. product has an API gravity of 49.2 and an aniline point of 3l.2"- F. The process of this invention; is particularly adapted to the production of olefins; This is especially carbon and light gaseous hydrocarbons.
apparent:unonrstudy-orthe datasetrforth in the table above. Each; of -'the;1z, Ga'fiy i s very highly olefinic. By use of this system and method of; operation t is possible to produce cuts which are as much as 96% olefinic.
--Heavy residual; -oi1scan; also be converted to other types of reaction products by changing the reactionconditions-within conversion chamber 33. In some cases it is desirable to utilize low cost materials such as the heavy residual oils to produce water gas 'which'is used commercially as fuel gas.
The process which has-been described above is modified by'raising'the temperature within the conversion chamber to between 2000 F. and 2400 F. At a, temperature within thisrange the oil fog is uniformly spread over the area of the conversion chamber but the temperature is so high that: the hydrocarbon oil is cracked to form Steam which is injected into the conversion chamber 33 through inlet, conduits 47', 36, 28,-and 52 reacts with the carbonaceous material to form CO, H2, and CO2 by the well known water gas reaction. The following reactions take place upon passing steam over carbon at. a temperature within the above specified temperature range.
When steam is present during thethermal cracking of the oil fog the above reactions are important along with reactions of hydrocarbons and steam. The reactions of methane and steam may be repreesented as follows:
A still further modification of thisinvention is made when it is desired to convert the heavy residual oils to form carbon black. Once again it is necessary-in the-modification of the process to change the reaction conditons by raising the temperature of the pebbles within conversion chamber 33. Inthis case it is necessary to maintain the temperature within the range of between 2300-F. and 2800 F. When producing carbon black it is desirable to utilize a diluent material other than steam for aiding the dispersion of oil fog with n the conversion chamber. For that reason a diluent materiaLsuch as hydrogen or methane, isintroduced into conversion chamber 33 throughinlet conduit 41. The product efiiuent is removed fromthe upper portion of conversion chamber 33 through 'efiluent conduit 54 and a quench material, such as water or methane, is utilized to lower the temperature of the efiiuent stream to a temperature between about 900 F. and 1100 F. The reaction product stream, together with the quench material, 'is introduced tangentially into separator 55 and heavy materials which are separated from the gas stream are removed therefrom through outlet conduit 58. Flow control valve 62 is closed and flow control valve 64 is opened so that the gaseous material which is removed from separator 55 through conduit 59. passes by way of' conduit '63 to electrostatic separator 65. The'carbon black is electrostatically precipitated from the gas stream within separator 65 and. is removed therefrom by means of conduit 66. The remaining gaseous products and, quench materialare removed from separator 65 through conduit 61 and are passed to manufacture of water gas as well as others heretofore set-forth. Pebbles which are at such a high temperature are verydiflicult to recycle from a conversion chamber to a pebble heatingchamber.
The amount of fluid material which is introduced .into thelower portion of the conversion chamber as a diluent can be varied so as to control the temperature of the recycled pebbles.
The process of this invention may be varied advantageously by utilizing only the flashed vapors as reactant materials and using those vapors to atomize a water stream so as to distribute the water particles through the lower portion of the conversion chamber. Referring particularly to the system shown as Figure 4 of the drawings, pebbles are heated in chamber 4| as heretofore described and are gravitated into conversion chamber 33. The pebbles are separated from the walls of a lower portion of the conversion chamber so as to form a void space therein. Hydrocarbon vapors are introduced into fog nozzles 29 as described above. Water is introduced into fog nozzles 29 through conduit 9|. The water is atomized by the vapor stream and the water particles, together with the hydrocarbon vapors, are introduced intothe void space formed in the lower portion of conversion chamber 33. The water particles are converted to steam within the lower portion of conversion chamber 33 and the steam, together with the hydrocarbon vapors,
pass upwardly through the hot pebble bed within the conversion chamber, the steam acting as a diluent for the hydrocarbon vapors. The hydrocarbon vapors are converted to the desired products within conversion chamber 33 and the gaseous products, together with the steam effluent, are removed from the upper portion of conversion chamber 33 through gaseous effluent outlet conduit 54. A quench material, such as water, is introduced into gaseous eflluent outlet conduit 54 through conduit 92 and the resulting mixture of fluids is introduced into separation chamber 93 where coke and tar are removed from the stream, The coke and tar are removed through v outlet conduit 94 in the lower portion thereof. The fluid stream is removed from chamber 93 and passed by a continuation of conduit 54 into cooler chamber 95 in which the stream is passed in heat exchange relation with a coolant fluid. The cooled stream is passed by further continuation of conduit 54 through condenser chamber 96 in which the eflluent stream is further cooled so as to condense the gaseous materials. The necessity for this condenser chamber will depend upon the amount of cooling obtained in cooler chamber 95.
The eifluent fluid stream is introduced into sepacon d uit 4ii. This type of operation has many advantages turned to the uppefportion of pebble heater chamber 4| through conduit 48, elevator fi'lpand over the operation of a' system in which "live steam is used asthe diluent material. A considerably greater amount of heat is removed from the-pebbles by the conversion of water to steam "within the conversion chamber than wouldfbe obtained by the introduction of a similar amount of steam into that chamber. It is thus possible "to utilize very high temperatures within the conversionchamber and yet lower the temperature of those pebbles before it is necessary to handle them in the recycle system to the pebble heater chamber. Very high thermal efliciency of the pebble heater system is therefore obtained by conversion chamber is condensed and circulated,
over and over again which makes it possible in areas in which water is scarce or is quite corrosive to treat a small amount of water and utilize that small amount of water continuously. The atomization of water with the flashed oil vapors makes possible a good distribution of the water through the conversion zone before it is transformed to steam.
Various other modifications and advantages of the process of this invention will be apparent to those skilled in the art upon study of the accompanying disclosure and the drawings. It is believed that such modifications are within the spirit and scope of this disclosure and the claims.
I'claim:
1. An improved residuum conversion system comprising an upright pebble heater chamber having pebble inlet means and efliuent outlet means in its upper end portion; heating material inlet means in the lower portion of said pebble heater chamber; an upright conversion chamber disposed below said pebble heater chamber; a pebble conduit extending between the lower end portion of said pebble heater chamber and the upper end portion of said conversion chamber; a perforate pebble support member extending inwardly from the wall of said conversion chamber at a level intermediate its ends, said pebble support member providing a pebble passage centrally therethrough; pebble outlet means in the lower portion of said conversion chamber; an elevator extending from said pebble outlet means in said conversion chamber to said pebble inlet means in said pebble heater chamber; at least one fog nozzle extending through the wall of said conversion chamber and adjacent the lower side of said pebble support member; an oil residuum heating chamber having residuum conduit means extending therethrough; a flash chamber; a conduit extending from said residuum conduit means in said residuum heating chamber to a point intermediate the ends of said flash chamber; a gaseous material conduit extending between the upper end of said flash chamber and the inlet end of said fog nozzle; a liquid material conduit extending from the bottom of said flash chamber to said fog nozzle; and a gaseous eifiuent outlet in the upper portion of said conversion chamber.
2. The system of claim 1, wherein a gaseous diluent 1nlet conduit is connected to said residu- A a iqj een said flash a 1 .1 v. h inlet conduitmans extend through and are ad- Number "iiereig -ihjjgilg 51.33;" mpaeem

Claims (1)

1. AN IMPROVED RESIDUUM CONVERSION SYSTEM COMPRISING AN UPRIGHT PEBBLE HEATER CHAMBER HAVING PEBBLE INLET MEANS AND EFFUENT OUTLET MEANS IN ITS UPPER END PORTION; HEATING MATERIAL INLET MEANS IN THE LOWER PORTION OF SAID PEBBLE HEATER CHAMBER; AN UPRIGHT CONVERSION CHAMBER DISPOSED BELOW SAID PEBBLE HEATER CHAMBER; A PEBBLE CONDUIT EXTENDING BETWEEN THE LOWER END PORTION OF SAID PEBBLE HEATER CHAMBER AND THE UPPER END PORTION OF SAID CONVERSION CHAMBER; A PERFORATE PEBBLE SUPPORT MEMBER EXTENDING INWARDLY FROM THE WALL OF SAID CONVERSION CHAMBER AT A LEVEL INTERMEDIATE ITS ENDS, SAID PEBBLE SUPPORT MEMBER PROVIDING A PEBBLE PASSAGE CENTRALLY THERETHROUGH; PEBBLE OUTLET MEANS IN THE LOWER PORTION OF SAID CONVERSION CHAMBER; AN ELEVATOR EXTENDING FROM SAID PEBBLE OUTLET MEANS IN SAID CONVERSION CHAMBER TO SAID PEBBLE INLET MEANS IN SAID PEBBLE HEATER CHAMBER; AT LEAST ONE FOG NOZZLE EXTENDING THROUGH THE WALL OF SAID CONVERSION CHAMBER AND ADJACENT THE LOWER SIDE OF SAID PEBBLE SUPPORT MEMBER; AN OIL RESIDUUM HEATING CHAMBER HAVING RESIDUUM CONDUIT MEANS EXTENDING THERETHROUGH; A FLASH CHAMBER; A CONDUIT EXTENDING FROM SAID RESIDUUM CONDUIT MEANS IN SAID RESIDUUM HEATING CHAMBER TO A POINT INTERMEDIATE THE ENDS OF SAID FLASH CHAMBER; A GASEOUS MATERIAL CONDUIT EXTENDING BETWEEN THE UPPER END OF SAID FLASH CHAMBER AND THE INLET END OF SAID FOG NOZZLE; A LIQUID MATERIAL CONDUIT EXTENDING FROM THE BOTTOM OF SAID FLASH CHAMBER TO SAID FOG NOZZLE; AND A GASEOUS EFFLUENT OUTLET IN THE UPPER PORTION OF SAID CONVERSION CHAMBER.
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Cited By (13)

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Publication number Priority date Publication date Assignee Title
US2760915A (en) * 1952-07-09 1956-08-28 Socony Mobil Oil Co Inc Method and apparatus for spraying a hydrocarbon feed oil in a moving bed hydrocarbonconversion system
US2789149A (en) * 1954-03-24 1957-04-16 Lummus Co Acetylene production
US2794771A (en) * 1953-07-09 1957-06-04 Socony Mobil Oil Co Inc Preliminary hydrocarbon conversion of heavy hydrocarbon oils for use in catalytic cracking
US2866836A (en) * 1954-10-22 1958-12-30 Phillips Petroleum Co Process and apparatus for conversion of hydrocarbons
DE975726C (en) * 1954-04-06 1962-06-28 Houdry Process Corp Process for splitting hydrocarbon residues
US4520224A (en) * 1982-03-11 1985-05-28 Mitsubishi Jukogyo Kabushiki Kaisha Thermal cracking method for producing olefins from hydrocarbons
US4853189A (en) * 1987-01-23 1989-08-01 Phillips Petroleum Company Apparatus for conversion of oils to hydrocarbon products
US4944845A (en) * 1987-11-05 1990-07-31 Bartholic David B Apparatus for upgrading liquid hydrocarbons
US4960502A (en) * 1987-01-23 1990-10-02 Phillips Petroleum Company Process for conversion of oils to hydrocarbon products
US6303842B1 (en) 1997-10-15 2001-10-16 Equistar Chemicals, Lp Method of producing olefins from petroleum residua
US20050053889A1 (en) * 2002-09-12 2005-03-10 Fraser Kevin S Method and apparatus for heating a slurry to a predetermined temperature
US20110143296A1 (en) * 2008-07-24 2011-06-16 Hatch Ltd. Method and apparatus for temperature control in a reactor vessel
US10570345B2 (en) * 2011-11-08 2020-02-25 Exxonmobil Chemical Patents Inc. Regenerative reactor system

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Publication number Priority date Publication date Assignee Title
US2146553A (en) * 1932-07-22 1939-02-07 Tide Water Associated Oil Comp Vapor-phase cracking process and the production of fog
US2432962A (en) * 1946-06-20 1947-12-16 Socony Vacuum Oil Co Inc Process for heating hydrocarbons by contact with alioving granular solid
US2437383A (en) * 1946-05-02 1948-03-09 Socony Vacuum Oil Co Inc Cracking process
US2492999A (en) * 1947-09-26 1950-01-03 Houdry Process Corp Method of and apparatus for minimizing deposition of carbonaceous material
US2574489A (en) * 1947-12-19 1951-11-13 Houdry Process Corp Process of converting hydrocarbon material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2146553A (en) * 1932-07-22 1939-02-07 Tide Water Associated Oil Comp Vapor-phase cracking process and the production of fog
US2437383A (en) * 1946-05-02 1948-03-09 Socony Vacuum Oil Co Inc Cracking process
US2432962A (en) * 1946-06-20 1947-12-16 Socony Vacuum Oil Co Inc Process for heating hydrocarbons by contact with alioving granular solid
US2492999A (en) * 1947-09-26 1950-01-03 Houdry Process Corp Method of and apparatus for minimizing deposition of carbonaceous material
US2574489A (en) * 1947-12-19 1951-11-13 Houdry Process Corp Process of converting hydrocarbon material

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2760915A (en) * 1952-07-09 1956-08-28 Socony Mobil Oil Co Inc Method and apparatus for spraying a hydrocarbon feed oil in a moving bed hydrocarbonconversion system
US2794771A (en) * 1953-07-09 1957-06-04 Socony Mobil Oil Co Inc Preliminary hydrocarbon conversion of heavy hydrocarbon oils for use in catalytic cracking
US2789149A (en) * 1954-03-24 1957-04-16 Lummus Co Acetylene production
DE975726C (en) * 1954-04-06 1962-06-28 Houdry Process Corp Process for splitting hydrocarbon residues
US2866836A (en) * 1954-10-22 1958-12-30 Phillips Petroleum Co Process and apparatus for conversion of hydrocarbons
US4520224A (en) * 1982-03-11 1985-05-28 Mitsubishi Jukogyo Kabushiki Kaisha Thermal cracking method for producing olefins from hydrocarbons
US4853189A (en) * 1987-01-23 1989-08-01 Phillips Petroleum Company Apparatus for conversion of oils to hydrocarbon products
US4960502A (en) * 1987-01-23 1990-10-02 Phillips Petroleum Company Process for conversion of oils to hydrocarbon products
US4944845A (en) * 1987-11-05 1990-07-31 Bartholic David B Apparatus for upgrading liquid hydrocarbons
US6303842B1 (en) 1997-10-15 2001-10-16 Equistar Chemicals, Lp Method of producing olefins from petroleum residua
US20050053889A1 (en) * 2002-09-12 2005-03-10 Fraser Kevin S Method and apparatus for heating a slurry to a predetermined temperature
US6945775B2 (en) 2002-09-12 2005-09-20 Hatch, Ltd. Method and apparatus for heating a slurry to a predetermined temperature
US20110143296A1 (en) * 2008-07-24 2011-06-16 Hatch Ltd. Method and apparatus for temperature control in a reactor vessel
US9322076B2 (en) * 2008-07-24 2016-04-26 Hatch Ltd. Method and apparatus for temperature control in a reactor vessel
US10570345B2 (en) * 2011-11-08 2020-02-25 Exxonmobil Chemical Patents Inc. Regenerative reactor system

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